Chloroaliphatic-monocarboxylic acid esters of 1, 4, 5, 6, 7, 7 hexachloro bicyclo-[2. 2. 1]-hept-5-en-2-methanol



- A a 2,802,862 Ice Patented Aug. 13, 1957 The following examples illustrate the invention but are 2,802,862 not to be construed as limiting: CHIflROALIPHATlC-MONOCARBOXYLIC ACID Example I.I,4,5,6,7,7-hexachlorobicycl0[2.2.1Jhept-5- ESTERS 0F l,4,5,6,7,7 HEXACHLORO BICYCLO- 5 en-Z-ylmerhyl a,a,fl-dichloropropionate [2.2.11-HEPT-5-EN-2-METHANOL c1 Herman 0. Senkbeil, Midland, Mich., assignor to The Dow Chemical Company, Midland, M611, 2 corpora- CFC/e/l;\climmghoqkfl(PCBl tion of Delaware (ll-l 31H: No Drawing. Application July 2, 1956, \(L/ Serial No. 595,071 in 4 Claims. (Cl. 260-487) A mixture of 75 grams (0.52 mole) of tx,a-dlChl01'0- The present invention is directed to the chloroaliphatic- Proplohic h 1555 grams mole) of monocarboxylic acid esters having the formula 7,7 Q h f p -f h solved in 200 milliliters of ethylene dichloride was heated at a temperature of from 107 to 118 C. for 68 hours.

During the heating period, the water of reaction as formed c1 c L ;cn cn, 0 n was removed by distillation as a mixture with some of 01-1 the solvent. Upon completion of the reaction, the reaction mixture was washed several times with water and f the washed mixture fractionally distilled under reduced 0: pressure to separate the desired ester product. This product boiled at 146152 C. at 0.5 millimeter pressure and had a chlorine content of 62.51 percent comto 5 carbon atoms inclusive These compounds are pared to the calculated chlorine content of 62.25 perviscous liquids somewhat soluble in many organic solvents and of low solubility in water. They have been Example 2.l,4,5,6,7,7-hexachlorobicyclo[2.2.1Mew-5- in which R represents a chloroacyl radical of the chloroalkanoic monocarboxylic acid series containing from 2 found to be active as herbicides and are adapted to be en-Z-ylmethyl a ,fl-rrichioroprapiortate employed in dust and spray compositions for the control m of the growth and the killing of weeds and for the sterilization of soil with regard to the growth of plants. They are also useful as parasiticides for the control of Ol-0 l CHCH;OCCC1a-CH:CI many insect and bacterial organisms. 03*! The new compounds may be prepared by reacting \i/ 1,4,5,6,7J-hexachlorobicyclo [2.2. 1 Jhept-S-en-Z-methanol with a chloroaliphatic-monocarboxylic acid such as a (111 chloroacetic acid, a chloropropionic acid, a chlorohutyric In a simigar manner to that described in Example 1,

acidPr a chlomvaleric acidreafifion may be carried 40 0.5 mole of a,e,fl-trichloropropionic acid and 0.5 mole of out In the Presence of an estenficanon catalyst such as 1,4,5,6,7,7-hexachlorobicyclo{2.2.IJhe t-S-en-Z-methanOl l i acid Phenol sulfonic acid P a f exchaflge were dissolved in 200 milliliters of ethylene dichloride and resin in the acid form, and conveniently in a water-imheated with still-33$ The mating was can-Ed out at a miscible solvent such as ethylene dichloride or toluene. temperature f f o to Q f a period f 91 The amount of feflctams P WQ is m -3 Since hours. The reaction mixture was then washed with wasome the deslred Pwdnct 1S produce! with any ter and fractionally distilled under reduced pressure. The proportion of reagents Good results are Obtamed when desired ester product boiled at 1s2-157" c. at 0.1 milsubstantially equimolecular proportions of the reactants meter pressure and was f d to contain 5p; percent an? P ?Y The p fy h of an excess of the chlorine compared to the calculated value of 65.14 perroahphattc monocarboxyhc acid and the removal of the cent.

water of reaction as formed generally results in optimum yields. Example 3.1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5- In carrying out the reaction, the alcohol, acid and en'zylmethyh"mdchlorobmymte catalyst, if employed, are mixed and the resulting mixture 0 heated at a temperature of from 75 to 150 C. for a sufiicient period of time to complete the reaction. In an alternative method, the reactants and catalyst, if em-- 01-0 ployed, may be dispersed in the solvent and the resulting (II- 43H,

mixture heated at the boiling temperature. During the L heating, a mixture of water of reaction and some of the A solvent are continuously removed by distillation, con- 1 densed and the sglvent rgcove cti A mixture Of 20 grams mole) Of 1,4,5,6,7,7-hex- Upon completion of the reaction, the desired product aChIOTDbiCYCIQIZ'Z-Ilhelil-5-en-2-meihanol, 11.8 grams may be separated by fractional distillation under reduced mole) of fl' y acid and milliliter pressure, Alternatively, th ol e t i t f th reacof concentrated sulfuric acid was dissolved in 100 miltion product is neutralized with an alkali such as dilute liters of ethylene dichloride- The resulting mixture aqueous sodium carbonate. The resulting mixture divides was heated at a temperature of from {0 or into aqueous and solvent layers. The solvent layer which a Period of 20 During the healing P the contains the st r reaction prgduct i separated d water of reaction was continuously removed as formed washed several times with water. The washed mixture from the reaction Vessel as a u e Wi h ome of the is then fractionally distilled under reduced pressure to solvent. The reaction mixture was then washed with waseparate the desired ester compound. ter and the ethylene dichloride was removed by distillation under reduced pressure. The desired product was obtained as a viscous liquid residue having a saponification equivalent of 470 and a chlorine content of 60.1 percent as compared to a theoretical equivalent of 470 and a theoretical chlorine content of 60.37 percent.

Example 4.1,4,5,6,7,7-hexachlorbicyclo[2.2.1]hept-5- en-Z-ylmethyl trichloroacetate This compound is prepared as described in Example 3 by the reaction of equimolecular proportions of trichloroacetic acid and l,4,5,6,7,7-hexachlorobicyclo[2.2.1lhept- S-en-Z-methanol in 200 milliliters of ethylene dichloride using sulfuric acid as a catalyst. The ester compound is a viscous liquid having a molecular weight of 476.

Example 5 .--1 ,4,5 ,6 ,7,7-hexachl0r0bicyclo[2.2.1 kept-5- en-Z-ylmethyl a,a,fl-dichlorova1erate Example 6 .-1 ,4,5 ,6,7,7-hexachlorobicycloi2.2.1 1 hept-S en-Z-ylmethyl a,a,fi-trichlarobutyrate The method described in Example 3 is employed to prepare this compound by the reaction of one mole of mafitrichlorobutyric acid boiling at 236 to 238 C. and one mole of 1,4,5,6,7,7-hexachlorobicyclo[2.2.1lhept-S-en-Z- methanol using toluene as a solvent and sulfuric acid as a catalyst. This ester compound has a molecular weight of 505.

The new ester compounds of the present invention have been tested and found to be effective as herbicides and parasiticides and particularly valuable for the killing of nematodes. For such use the products may be dispersed on an inert finely divided solid and employed as dusts. Also, such mixtures may be dispersed in water with the aid of a wetting agent and employed as sprays. In other procedures, the products may be employed as constituents of oil-in-water emulsions or water dispersions with or without the addition of wetting, dispersing or emulsifying agents. In representative operations, complete controls of rootknot nematodes are obtained when the nematodes are contacted with aqueous compositions containing 10 parts by weight of l,4,5,6,7,7- hexachlorobicyclo[2.2.1]hept-5-en-2-ylmethyl nae-dichloropropionate per million parts by Weight of ultimate mixture.

l,4,5,6,7,7-hexachlorobicyclo[2.2.llhept-S-en-2-methanol employed as a starting material as herein described is a commercially available alcohol melting at 162 to 162.5 C. and having a molecular weight of 331. This alcohol may be prepared by a Diels-Alder reaction wherein hexachlorocyclopentadiene is condensed with allyl alcohol at a temperature of from about 100 to 150 C.

The preferred esters of the present invention are those prepared from acids such as dichloroacetie acid, trichloroacetic acid, m,a-dichloropropionic acid, u,a,fi-trichloropropionic acid, a,a-dichlorobutyric acid and camdichlorovaleric acid. Such compounds may be characterized by the formula L 01-0 CH-CHaO-A 1]) Cl: (31- L H:

wherein A represents a,a-dichloroacyl or a,a,p-trichloroacyl in which said acyl is of the lower aliphatic series.

I claim:

1. A chloroaliphatic-monocarboxylic acid ester having the formula References Cited in the file of this patent Fields: I. Am. Chem. Soc. 76 (1954), 2709-10.

McBee et aL: I. Am. Chem. Soc. 77 (1955), 4427-8. 

1. A CHLOROALIPHATIC-MONOCARBOXYLIC ACID ESTER HAVING THE FORMULA 